US4987219A - Copolymeric and amphiphilic polyimide precursor, process for preparing the same and thin film - Google Patents

Copolymeric and amphiphilic polyimide precursor, process for preparing the same and thin film Download PDF

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US4987219A
US4987219A US07/041,275 US4127587A US4987219A US 4987219 A US4987219 A US 4987219A US 4127587 A US4127587 A US 4127587A US 4987219 A US4987219 A US 4987219A
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precursor
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Masakazu Uekita
Hiroshi Awaji
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Kanegafuchi Chemical Industry Co Ltd
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Assigned to KANEGAFUCHI KAGAKU KOGYO KABUSHIKI KAISHA, 2-4, NAKANOSHIMA 3-CHOME, KITA-KU, OSAKA-SHI, JAPAN reassignment KANEGAFUCHI KAGAKU KOGYO KABUSHIKI KAISHA, 2-4, NAKANOSHIMA 3-CHOME, KITA-KU, OSAKA-SHI, JAPAN ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: AWAJI, HIROSHI, UEKITA, MASAKAZU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/20—Processes for applying liquids or other fluent materials performed by dipping substances to be applied floating on a fluid
    • B05D1/202—Langmuir Blodgett films (LB films)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides

Definitions

  • the present invention relates to a copolymeric and amphiphilic precursor of polyimide, a process for the preparation thereof, and thin films, and more particularly to a copolymeric amphiphilic polyimide precursor modified so as to form a film by the Langmuir-Blodgett technique.
  • LB film Langmuir-Blodgett films
  • films of polyimide have excellent heat resistance.
  • the thickness of the films prepared, for instance, by spin coating is at least 1,000 ⁇ , usually 1 ⁇ m or more. It is very difficult to form a heat resistant polyimide film with a thickness of less than 1,000 ⁇ and with no pin-hole.
  • a further object of the present invention is to provide a material capable of providing a heat resistant ultrathin film.
  • a still further object of the present invention is to provide ultrathin films of copolymeric polyimides.
  • a polyamide acid can form a film by introducing substituent groups for imparting the hydrophobic property to a polyamide acid into the polyamide acid by means of Langmuir-Blodgett technique, and ultrathin polyimide films with heat resistance over 400° C. can be produced by imidizing the multilayer films of the so modified polyamide acid.
  • a copolymeric amphiphilic polyimide precursor having the recurring unit of the formula (1): ##STR2## wherein R 1 is a tetravalent group having at least 2 carbon atoms, R 2 is a bivalent group having at least 2 carbon atoms, and R 3 , R 4 , R 5 and R 6 are hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from the group consisting of an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an aromatic group or an alicyclic group, and their groups substituted by a halogen atom, nitro group, amino group, cyano group, methoxyl group or acetoxyl group, provided that at least one of R 3 , R 4 , R 5 and R 6 is neither hydrogen atom nor the above-mentioned group which has 1 to 11 carbon atoms;
  • copolymeric and amphiphilic polyimide precursors of the invention are as follows:
  • R 2 , R 5 and R 6 are as defined above, at a temperature of not lower than -10° C.
  • copolymeric and amphiphilic polyimide precursor of the invention having a recurring unit of the formula (3): ##STR7## wherein R 8 is a trivalent group having at least 2 carbon atoms, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , x and y are as defined above;
  • R 2 , R 5 and R 6 are as defined above at a temperature of not lower than -10° C.
  • the copolymeric and amphiphilic polyimide precursor of the invention having a recurring unit of the formula (4): ##STR12## wherein R 9 is a trivalent group having at least 2 carbon atoms, X is a substituent group of R 9 , and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , x and y are as defined above;
  • R 2 , R 5 and R 6 are as defined above and a compound of the formula (16): ##STR15## wherein R 5 , R 6 , R 9 and X are as defined above at a temperature of not lower than -10° C.
  • the copolymeric and amphiphilic polyimide precursor of the invention having a recurring unit of the formula (5): ##STR16## wherein R 10 is a tetravalent group having at least 2 carbon atoms, X and Y are substituent groups of R 10 , and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , x and y are as defined above;
  • R 2 , R 5 and R 6 are as defined above, and a compound of the formula (17): ##STR19## wherein R 5 , R 6 , R 10 , X and Y are as defined above at a temperature of not lower than -10° C.
  • the copolymeric and amphiphilic polyimide precursor of the invention having a recurring unit of the formula (19): ##STR20## wherein R 11 and R 12 are hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from the group consisting of an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an aromatic group or alicyclic group, and their groups substituted by a halogen atom, nitro group, amino group, cyano group, methoxyl group or acetoxyl group, provided that at least one of R 11 and R 12 is neither hydrogen atom nor the above-mentioned group which has 1 to 11 carbon atoms, and R 1 , R 2 , R 8 , x and y are as defined above;
  • R 2 , R 11 and R 12 are as defined above at a temperature of not higher than 50° C.
  • copolymeric and amphiphilic polyimide precursor of the invention having a recurring unit of the formula (21): ##STR23## wherein R 1 , R 2 , R 9 , R 11 , R 12 , X, x and y are as defined above is prepared by a process in which a tetracarboxylic acid dianhydride of the formula (10): ##STR24## wherein R 1 is as defined above and a compound of the formula (18):
  • R 2 , R 11 and R 12 are as defined above are reacted with a compound of the formula (20): ##STR25## whereinR 9 , R 11 and R 12 are as defined above at a temperature of not higher than 50° C.
  • copolymeric and amphiphilic polyimide precursor of the invention having a recurring unit (23): ##STR26## wherein R 1 , R 2 , R 10 , R 11 , R 12 , X, Y, x and y are as defined above is prepared by a process in which a tetracarboxylic acid dianhydride of the formula (10): ##STR27## wherein R 1 is as defined above and a compound of the formula (18):
  • R 2 , R 11 and R 12 are as defined above are reacted with a compound of the formula (22): ##STR28## wherein R 10 , R 11 , R 12 , X and Y are as defined above at a temperature of not higher than 50° C.
  • FIG. 1 is an infrared absorption spectrum (hereinafter referred to as "IR absorption spectrum") of the copolymeric and amphiphilic polyimide precursor of the present invention obtained in Example 1 described after;
  • FIG. 2 is a graph showing the result of thermal analysis (thermogravimetric analysis-differential thermal analysis) of the precursor obtained in Example 1;
  • FIG. 3 is a graph showing the results of thermal analysis (TGA-DTA) of the precursor having no 2,5-diaminobenzamide;
  • FIG. 4 is IR absorption spectrum of the precursor obtained in Comparative Example 2 described after;
  • FIG. 5 is a graph showing the results of 1 H nuclear magnetic resonance (hereinafter referred to as " 1 H NMR”) of the precursor obtained in Comparative Example 2;
  • FIG. 6 is a graph showing the results of thermal analysis of the precursor obtained in Comparative Example 2.
  • FIG. 7 is a graph showing the relationship between the inverse capacitance (1/c) of MIM devices prepared from a built-up film obtained in Example 3 and the number of layers (M) in the built-up film;
  • FIG. 8 is a graph showing the relationship between the inverse capacitance (1/c) of Al/copolymeric polyimide thin film/Al devices prepared from a built-up film obtained in Example 4 and the number of layers (M) in the built-up film;
  • FIG. 9 is an IR absorption spectrum of the precursor obtained in Example 5 described after.
  • FIG. 10 is a graph showing the results of thermal analysis (TGA-DTA) of the precursor obtained in Example 5;
  • FIG. 11 is a graph showing the relationship between the surface pressure ( ⁇ ) and the area per recurring unit of the precursor obtained in Example 5;
  • FIG. 12 is a graph showing the relationship between the inverse capacitance (1/c) of MIM devices prepared from a built-up film obtained in Example 7 and the number of layers (M) in the built-up film;
  • FIG. 13 is a graph showing the relationship between the inverse capacitance (1/c) of Al/copolymeric polyimide thin film/Al devices prepared from a built-up film obtained in Example 8 and the number of layers (M) in the built-up film.
  • the copolymeric and amphiphilic polyimide precursors of the present invention are polymers having the recurring unit of the formula (1): ##STR29## wherein the groups R 1 to R 6 are as defined above, and a part of at least one of R 1 and R 2 is substituted with a group having a valence different therefrom, and having a number average molecular weight of 2,000 to 300,000, preferably from 10,000 to 150,000.
  • the precursor has a tendency that the strength of the film prepared therefrom is too low, or that the viscosity thereof is too high and accordingly the procedure for forming LB films becomes difficult.
  • R 1 is a tetravalent group having at least two carbon atoms, preferably from 5 to 20 carbon atoms It may be an aromatic group; an alicyclic group; a aliphatic group; a group wherein an aromatic group and an aliphatic group are combined; a group wherein each of the above-mentioned groups is substituted by a monovalent group having 1 to 30 carbon atoms selected from the group consisting of an aliphatic group, an alicyclic group, an aromatic group, and a group in which an aliphatic group is combined with an aromatic group or alicyclic group; or a group wherein each of the preceding groups is substituted by a monovalent group such as a halogen atom, nitro group, amino group, cyano group, methoxyl group or acetoxyl group, or by a group in which the above monovalent group bonds to --O--, --COO--, --NHCO--, --CO--, --S--, --
  • R 1 is, for instance, ##STR30## or the like.
  • benzenoid unsaturation is a technical term used in contradistinction to the quinoid structure, as shown below, and means structures same as those of carbon rings included in usual aromatic compounds. ##STR31##
  • the positions of four bonds of the group R 1 are not particularly limited. However, it is preferable that each two of these four bonds are present at adjacent two carbon atoms constituting the group R 1 , since a five-membered or six-membered ring is easy to be formed when a film formed from the copolymeric polyimide precursor is ring-closed.
  • the group of the formula: ##STR34## is also preferable as the group R 1 .
  • the group R 2 in the formula (1) is a bivalent group having at least 2 carbon atoms. It may be an aromatic group; an aliphatic group; an alicyclic group; a group wherein an aromatic group and an aliphatic group are combined; a group wherein each of the above-mentioned bivalent groups is substituted by a monovalent group having 1 to 30 carbon atoms selected from the group consisting of an aliphatic group, an alicyclic group, an aromatic group and a group in which an aliphatic group is combined with an alicyclic group or an aromatic group; or a group wherein each of the preceding groups is substituted by a monovalent group such as a halogen atom, nitro group, amino group, cyano group, methoxyl group or acetoxyl group, or by a group in which the above monovalent group bonds to --O--, --COO--, --NHCO--, --CO--, --S--, --CSS--, --NHCS--
  • R 2 are, for example, ##STR36## wherein R 13 is as defined above, and the like.
  • Each of the groups R 3 , R 4 , R 5 and R 6 in the formula (1) is hydrogen atom or a monovalent group having 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, such as a monovalent aliphatic group, a monovalent alicyclic group, a monovalent aromatic group, a monovalent group in which an aliphatic group is combined with an aromatic group or an alicyclic group, or their halogen, nitro, amino, cyano, methoxy or acetoxy substituted groups.
  • R 3 , R 4 , R 5 and R 6 are groups introduced in order to impart a hydrophobic property to a polyamide acid having the recurring unit of the formula (24): ##STR37## wherein R 1 and R 2 are as defined above.
  • R 3 , R 4 , R 5 and R 6 preferably at least two of them, more preferably two of them, are neither hydrogen atom nor the above defined groups having 1 to 11 carbon atoms, preferably 1 to 15 carbon atoms, in other words, at least one of R 3 , R 4 , R 5 and R 6 , preferably at least two of them, are a monovalent group having 12 or more carbon atoms, preferably 16 or more carbon atoms, selected from the above defined groups.
  • n is an integer of 12 to 30, preferably 16 to 22, and the like.
  • At least one, preferably at least two, of the groups R 3 , R 4 , R 5 and R 6 is a straight-chain alkyl group of the formula: ##STR39## wherein n is as defined above, from the viewpoint of performances and cost. It is not essential that the substituent group, i.e. halogen atom, nitro group, amino group, cyano group, methoxyl group or acetoxyl group, as mentioned above is included in the groups R 3 , R 4 , R 5 and R 6 . But it is preferable that fluorine atoms are included in the groups R 3 , R 4 , R 5 and R 6 , because fluorine atoms vastly improve the hydrophobic property as compared with hydrogen atoms.
  • the copolymer useful as the amphiphilic polyimide precursor has the recurring unit of the formula (1): ##STR40## wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined above; a part of at least one of the groups R 1 and R 2 being substituted with a group having a valence different from each of the substituted R 1 and R 2 .
  • the substituent group is selected from groups other than tetravalent groups, that is, bivalent groups and trivalent groups can be employed. Among them, trivalent groups are preferable from the point of heat resistance.
  • the polyimide precursor has the recurring unit of the formula (2) or (3): ##STR41## wherein the groups R 1 to R 6 , x and y are as defined above, and R 7 and R 8 are respectively a bivalent group or a trivalent group having at least 2 carbon atoms.
  • the substituent group is selected from groups other than bivalent groups. It is preferable to use trivalent groups or tetravalent groups.
  • the polyimide precursor has the recurring unit of the formula (4) or (5): ##STR42## wherein the groups R 1 to R 6 are as defined above, each of R 9 and R 10 is a trivalent group or a tetravalent group having at least 2 carbon atoms, and X and Y are substituent groups bonded to the group R 9 or R 10 .
  • X and Y are, for instance, --NHR', --CONHR' --SO 2 NHR' wherein R' is an alkyl group or hydrogen atom, and the like.
  • the modification of the amphiphilic polyimide precursor of the present invention is important for improving the built-up property in Langmuir-Blodgett technique and the property of polyimide thin film obtained by ring-closing the built-up layer on a substrate. Particularly, when a part of the group R 2 is substituted with trivalent or tetravalent groups, a ring structure whose heat resistances is expected to be better than that of the imide ring is formed.
  • the groups R 7 to R 10 are bivalent, trivalent and tetravalent groups having at least 2 carbon atoms, preferably 5 to 20 carbon atoms They may be an aromatic group; an alicyclic group; an aliphatic group; a group wherein an aromatic group and an aliphatic group are combined; a group wherein each of the above-mentioned groups is substituted by a monovalent group having 1 to 30 carbon atoms selected from the group consisting of an aliphatic group, an alicyclic group, an aromatic group, and a group in which an aliphatic group is combined with an aromatic group or alicyclic group; or a group wherein each of the preceding groups is substituted by a monovalent group such as a halogen atom, nitro group, amino group, cyano group, methoxyl group or acetoxyl group, or by a group in which the above monovalent group bonds to --O--, --COO--, --NHCO--, --CO--, --S-
  • R 7 , R 8 , R 9 and R 10 are, for instance, ##STR43##
  • the positions of three or four bonds of the groups R 8 , R 9 and R 10 that is to say, the positions of the bonds linkingR 3 ##STR45## X and Y, to the recurring units (3) to (5) are not particularly limited. However, it is preferable that two from among these three or four bonds are present at adjacent carbon atoms constituting the groups R 8 , R 9 and R 10 , since a five-membered or six-membered ring is easy to be formed when a film formed from the copolymeric polyimide precursor is ring-closed.
  • the copolymeric and amphiphilic polyimide precursors of the present invention have the recurring unit of the following formulas: ##STR46## whereinR 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 are as defined above, provided that R 3 and R 4 are neither hydrogen atoms nor a group having 1 to 11 carbon atoms, and X, Y, x and y are as defined above; ##STR47## whereinR 1 , R 2 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are as defined above provided that R 5 and R 6 are neither hydrogen atom nor a group having 1 to 11 carbon atoms and X, Y, x and y are as defined above.
  • the copolymeric and amphiphilic polyimide precursors having the recurring unit of the above formulas are advantageous in easiness of
  • copolymeric and amphiphilic polyimide precursor of the present invention having the above recurring unit are, for instance, those having the recurring unit of the formula: ##STR48## [in which typical examples of R 3 , R 4 , R 5 and R 6 are CH 3 (CH 2 ) 11 --, CH 3 (CH 2 ) 13 --, CH 3 (CH 2 ) 15 --, CH 3 (CH 2 ) 17 --, CH 3 (CH 2 ) 19 --, CH 3 (CH 2 ) 21 --, CF 3 (CH 2 ) 15 --, and the like], ##STR49## [in which typical examples of R 3 and R 4 are CH 3 (CH 2 ) 11 --, CH 3 (CH 2 ) 13 --, CH 3 (CH 2 ) 15 --, CH 3 (CH 2 ) 17 --, CH 3 (CH 2 ) 19 --, CH 3 (CH 2 ) 21 --, CF 3 (CH 2 ) 15 --, and the like], ##STR50## [in which typical examples of R 5 and R 6 are CH 3 (CH 2 )
  • R 3 and R 4 are, for instance, CH 3 (CH 2 ) 11 --, CH 3 (CH 2 ) 13 --, CH 3 (CH 2 ) 15 --, CH 3 (CH 2 ) 17 --, CH 3 (CH 2 ) 19 --, CH 3 (CH 2 ) 21 --, CF 3 (CH 2 ) 15 --, and the like
  • R 5 and R 6 are, for instance, CH 3 --, CH 3 (CH 2 ) 2 --, CH 3 (CH 2 ) 5 --, and the like]
  • the symbol “ ⁇ ” means isomerism.
  • the above formula represents both the recurring unit of the formula (a): ##STR53## and the recurring unit of the formula (b): ##STR54## and in such a case, the symbol " ⁇ " indicating the isomerism is used.
  • Various copolymers are provided when at least one of the groups R 1 to R 10 in the formulas (1) to (5) is at least two kinds of groups selected from the respective representative examples of the groups R 1 to R 10 explained above.
  • the precursors of the present invention include such a precursor.
  • the copolymeric and amphiphilic polyimide precursors of the present invention are soluble in an organic polar solvent such as N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide or hexamethylphosphoramide, are soluble in a mixed solvent of the above-mentioned organic polar solvent and a usual organic solvent such as chloroform, and are slightly soluble or insoluble in a usual organic solvent such as benzene, ether, chloroform, acetone or methanol.
  • organic polar solvent such as N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide or hexamethylphosphoramide
  • the precursors of the present invention may contain about 30% by mole of the recurring unit of the formula (25): ##STR55## wherein R 1 and R 2 are as defined above, R is a monovalent group having 1 to 11 carbon atoms selected from the group consisting of a monovalent aliphatic group, a monovalent alicyclic group, a monovalent aromatic group, a monovalent group in which an aliphatic group is combined with an aromatic group or an alicyclic group, and their substituted monovalent groups with a halogen atom, nitro group, amino group, cyano group, methoxyl group or acetoxyl group, or hydrogen atom, and four groups R may be the same or different.
  • copolymeric and amphiphilic polyimide precursors of the present invention having the recurring unit of the formula (1) can be prepared by the following method.
  • the precursor having the recurring unit of the formula (4) is prepared as follows:
  • the compound (11) is then converted into an acid halide, for instance, by reacting with thionyl chloride, phosphorus pentachloride, benzenesulfonyl chloride, or the like in a substantially anhydrous polar solvent at a temperature of not lower than -10° C., preferably about 0° to about 40° C.
  • the acid halide is reacted with a compound of the formula (15):
  • R 2 , R 5 and R 6 are as defined above, and the compound of the formula (16): ##STR58## wherein R 5 , R 6 , R 9 and X are as defined above.
  • the acid halide may be added to the compounds (15) and (16), or inversely the compounds (15) and (16) may be added to the acid halide.
  • the reaction of the acid halide and the compounds (15) and (16) is conducted at a temperature of not lower than -10° C., preferably 0° to 10° C., and may be conducted at a temperature of not lower than 20° C. to complete the reaction.
  • tetracarboxylic acid dianhydride (10) are, for instance: ##STR59## and the like.
  • R 3 OH and R 4 OH are, for instance, CH 3 OH, CH 3 CH 2 OH, CH 3 (CH 2 ) 2 OH, CH 3 (CH 2 ) 3 OH, CH 3 (CH 2 ) 5 OH, CH 3 (CH 2 ) 7 OH, CH 3 (CH 2 ) 9 OH, CH 3 (CH 2 ) 11 OH, CH 3 (CH 2 ) 13 OH, CH 3 (CH 2 ) 15 OH, CH 3 (CH 2 ) 17 OH, CH 3 (CH 2 ) 19 OH, CH 3 (CH 2 ) 21 OH, CH 3 (CH 2 ) 23 OH, CF 3 (CH 2 ) 15 OH, H(CF 2 ) 2 (CH 2 ) 15 OH, H(CF 2 ) 4 (CH 2 ) 13 OH, F(CF 2 ) 8 (CH 2 ) 2 OH, F(CF 2 ) 8 (CH 2 ) 4 OH, ##STR60## (CH 3 ) 3 C(CH 2 )
  • the reaction conditions for producing the compound (11) by the reaction of the tetracarboxylic acid dianhydride (10) with R 3 OH and R 4 OH are not particularly limited.
  • the reaction can be conducted in a manner in which the reaction system is stirred at about 100° C. for several hours in a nitrogen stream, or there are adopted general conditions such that the reaction is conducted with stirring at room temperature for about 4 days in a solvent such as hexamethylphosphoramide. From the viewpoint of shortening the reaction time, namely better productivity, it is advantageous that the reaction is conducted with stirring at an elevated temperature, e.g. about 100° C., for several hours, e.g.
  • the obtained compound (11) may be purified by a method such as recrystallization, prior to converting into the acid halide, for the purpose of improving the purity.
  • the polar solvents used in the reaction for converting the compound (11) into the acid halide there are mentioned, for instance, hexamethylphosphoramide, N,N-dimethylacetamide and N,N-dimethylformamide.
  • the solvents are used in a substantially anhydrous state. That is to say, the reaction for the conversion into the acid halide is conducted under an approximately quantitative condition such that thionyl chloride, phosphorus pentachloride, benzenesulfonyl chloride, or the like used in the reaction would not decompose by moisture.
  • the reaction temperature for the conversion into the acid halide is lower than -10° C.
  • the reaction becomes heterogeneous due to freezing of long chain alkyl groups.
  • the temperature is not lower than -10° C.
  • the temperature up to near the boiling point of the acid halide can be used without restriction.
  • the temperature within the range of about 0° to about 40° C. is preferable.
  • the thus prepared acid halide is then reacted with the compounds (15) and (16) to produce the precursor of the present invention. From the viewpoint of the workability, it is desirable to use the obtained acid halide as it is without any treatment.
  • both the reactants and the product tend to solidify by the long chain alkyl group of the groups R 3 , R 4 , R 5 and R 6 present in these compounds and, therefore, it is general to use a solvent such as N,N-dimethylacetamide or N,N-dimethylformamide.
  • the reaction temperature is not lower than -10° C., preferably from -10° to +20° C., more preferably from 0° to +10° C.
  • reaction temperature When the reaction temperature is lower than -10° C., the reaction becomes heterogeneous owing to freeze solidification.
  • the reaction temperature over 20° C. should be avoid in the initial stage of the reaction because it is considered that in the initial stage undesirable reactions are easy to occur.
  • the use of the reaction temperature over 20° C. in the latter stage of the reaction is advantageous in order to complete the reaction and in order to keep the reaction hemogeneous to the completion of the reaction.
  • Representative examples of the compound (15) are, for instance, ##STR62## whereinR 5 and R 6 are as defined above.
  • Representative examples of the groups R 5 and R 6 are, for instance, CH 3 --, CH 3 CH 2 --, CH 3 (CH 2 ) 2 --, CH 3 (CH 2 ) 3 --, CH 3 (CH 2 ) 5 --, CH 3 (CH 2 ) 11 --, CH 3 (CH 2 ) 13 --, CH 3 (CH 2 ) 15 --, CH 3 (CH 2 ) 17 --, CH 3 (CH 2 ) 19 --, CH 3 (CH 2 ) 21 --, CH 3 (CH 2 ) 23 --, CF 3 (CH 2 ) 15 --, H(CF 2 ) 2 (CH 2 ) 15 --, H(CF 2 ) 4 (CH 2 ) 13 --, F(CF 2 ) 8 (CH 2 ) 2 --, F(CF 2 ) 8 (CH 2 ) 4 --, and the like.
  • the ratio of the acid halide to the compounds (15) and (16) is suitably selected so as to produce the precursor having a desired molecular weight.
  • stoichiometric amounts of the purified monomers and a purified solvent have been used for obtaining the product having a high molecular weight.
  • a high molecular weight is not always required and even if the precursor has not a high molecular weight, sufficient characteristics can be exhibited.
  • the molar ratio of the reactants may deviate from stoichiometric one, and the acid halide and the compounds (15) and (16) can be used in a molar ratio of about 1/0.8 to about 1/1.2 without causing any problems.
  • both of the groups R 5 and R 6 in the compounds (15) and (16) may be hydrogen atom, and in that case, the precursors having the recurring unit represented by the formula (8) are obtained.
  • the use of the compound (15) in which both of the groups R 5 and R 6 are hydrogen atom, is advantageous in that the reactivity is good and the raw material cost is inexpensive.
  • the precursor since the --COOR 3 and --COOR 4 groups in the obtained precursor are in the state of ester, the precursor is thermally stable and the reaction scarcely proceeds in isolation and drying steps and, therefore, the precursor is separable in the form of solid powder and thus purification is easy.
  • the copolymeric and amphiphilic polyimide precursors of the present invention can be prepared by the process mentioned above.
  • the precursors of the present invention having the recurring unit having the formula (21) can be prepared by directly reacting the tetracarboxylic acid dianhydride (10) with a compound of the formula (18):
  • R 2 , R 11 and R 12 are as defined above, and a compound of the formula (20): ##STR64## wherein R 9 , R 11 , R 12 and X are as defined above.
  • the reaction can be made either in a manner in which the tetracarboxylic acid dianhydride (10) is added to the compounds (18) and (20) or in a manner in which the compounds (18) and (20) are added to the dianhydride (10).
  • Representative examples of the compound (18) are, for instance, ##STR65## wherein representative examples of the groups R 11 and R 12 are ##STR66## CF 3 (CH 2 ) 15 --, H(CF 2 ) 2 (CH 2 ) 15 --, H(CF 2 ) 4 (CH 2 ) 13 --, F(CF 2 ) 8 (CH 2 ) 2 --, H(CF 2 ) 8 (CH 2 ) 4 --, and the like.
  • the reaction is conducted in a substantially anhydrous organic polar solvent such as N,N-dimethylacetamide or N,N-dimethylformamide at a temperature of not higher than 50° C., preferably room temperature, using the compounds (18) and (19) in an amount of 0.8 to 1.2 moles per mole of the tetracarboxylic acid dianhydride (10). Even if the amounts of the reactants deviate from the stoichiometric amounts, the obtained precursors exhibit satisfactory characteristics.
  • a substantially anhydrous organic polar solvent such as N,N-dimethylacetamide or N,N-dimethylformamide
  • the thus prepared precursors of the present invention having the recurring unit (21) have also the features that they can form films by the LB method and provide polyimides by heating, in addition to easiness in preparation.
  • the precursors (2), (3) and (5) can be prepared in the same manner as in the preparation of the precursor (4).
  • the precursor (2) can be prepared by the following method.
  • the compound (11) and a compound having the formula (12): ##STR70## wherein R 7 is as defined above, are converted into acid halides in a substantially anhydrous polar solvent at a temperature of not lower than -10° C.
  • the acid halides are reacted with a compound of the formula (15):
  • R 2 , R 5 and R 6 are as defined above, at a temperature of not lower than -10° C. to produce the desired precursor (2).
  • the precursor having the recurring unit (3) can be produced by the following method.
  • R 2 , R 5 and R 6 are as defined above, at a temperature of not lower than -10° C. to produce the desired precursor (3).
  • the precursor having the recurring unit (5) can be produced by the following method.
  • the acid halide is reacted with a compound of the formula (15):
  • R 2 , R 5 and R 6 are as defined above, and a compound of the formula (17): ##STR77## wherein R 5 , R 6 , R 10 , X and Y are as defined above, at a temperature of not lower than -10° C. to produce the desired precursor (5).
  • LB films can be formed from the precursors of the present invention by any of the so-called LB technique without restriction, e.g. the vertical dipping method (LB method), the horizontal dipping method, the revolving cylindrical method and so on (as described in Shin Jikken Kagaku Koza, Vol. 18, “Interface and Colloid", pages 498-508).
  • the LB technique is a method in which a LB material is spread onto the surface of water and compressed at a constant surface pressure to form monomolecular layer film and the monomolecular layer is transferred onto a substrate.
  • a solvent such as benzene or chloroform which evaporates into a gas phase without dissolving in water, is used for spreading as LB film forming material onto the water surface.
  • a solvent such as benzene or chloroform which evaporates into a gas phase without dissolving in water, is used for spreading as LB film forming material onto the water surface.
  • organic polar solvent examples include, for instance, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetoamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylenesulfone, dimethyltetramethylenesulfone, and the like.
  • the concentration of the precursor solution to be spread onto the water surface is not particularly limited, but is usually selected from 2 ⁇ 10 -3 to 5 ⁇ 10 -3 M.
  • a built-up film is formed on a substrate by using a mixture of a known LB compound and the precursor of the invention, since film-forming properties are improved.
  • the substrates used for forming LB films of the precursors thereon are not particularly limited, and are selected according to the uses of the formed LB film. In case of converting the LB film into a copolymeric polyimide film by heating the LB film of the precursor, it is necessary that the substrates have a good heat resistance.
  • Examples of the substrate used in forming the LB films are, for instance, an inorganic substrate such as glass, alumina or quartz, a metal substrate, a plastic substrate, a substrate of a semiconductor of Groups IV, III-V, II-VI of the Periodic Table such as Si, GaAs or ZnS, a substrate of a ferroelectric substance such as PbTiO 3 , BaTiO 3 , LiNbO 3 or LiTaO 3 , a substrate of a magnetic substance, and the like.
  • the substrates may be surface-treated in a usual manner. Also, it is preferable to conduct surface-treatment to the surface of the substrate with a silane coupling agent.
  • the precursors of the present invention can form thin films having no or a little defect and having a good heat resistance by the LB method, and can provide thin films having a further improved heat resistance by partially or completely ring-closing the precursor thin film into a copolymeric polyimide.
  • Methods for ring-closure namely forming a five-membered ring or a six-membered ring such as imidizing are not particularly limited, but heating at a temperature of about 200° to about 500° C. is general.
  • the ring closure can also be conducted by using laser lights.
  • the ring-closure can be conducted by using acetic anhydride or pyridine used in the imidizing of polyamide acid or by using the above compound with heating.
  • Polyimides are produced from the precursors of the invention, for instance, according to the following reaction schemes with respect to the precursors (6), (7), (8) and (9). ##STR82## wherein x and y are as defined above.
  • the latter two structures are preferable since a skelton with good heat resistance is introduced into the recurring unit.
  • the polyamide acid representated by the formula (24) can be converted into polyimide with formation of H 2 O, but this polyamide acid (24) is not usable as a material for forming LB films.
  • the groups introduced for imparting the hydrophobic property to a polyamide acid eliminate in the form of an alcohol. Since the eliminated alcohol can be scattered away by conducting the ring closure in a gas stream or under vacuum at a temperature of about 200° to about 500° C., copolymeric polyimide films having excellent heat resistance and electric insulation property can be obtained.
  • the area-time curve clearly reveals that the copolymeric and amphiphilic polyimide precursors of the present invention form ideal Y-type films by the LB method (vertical depping method)
  • the linearity of the relationship between the inverse capacitance (1/C) and the number of layers (M) in the built-up film suggests that a layer structure expected to LB films is present in the built-up films of the copolymeric and amphiphilic polyimide precursors of the present invention.
  • the thin films of the precursors of the invention have good heat resistance, dielectric characteristics and electric insulation properties as well as an excellent controllability of film thickness. Therefore, the LB films of the precursors can be directly used for the various purposes such as electronic devices.
  • the copolymeric polyimide thin films obtained from the precursors of the present invention have excellent heat resistance and chemical resistance and good mechanical properties.
  • the thin film of the present invention is more excellent in heat resistance than known polyimide thin films formed from polyimide homopolymers previously proposed by us. Because of the linearity of the relationship between 1/C and the number of layers, the built-up film retains its excellent thickness controllability even after conversion into copolymeric polyimide, thus it is possible to control the thickness of copolymeric polyimide thin films on the basis of the number of layers in the built-up films of the precursors. Furthermore, it is assumed that a layer structure is present in the copolymeric polyimide thin films, and also it has been made clear that the copolymeric polyimide thin films prepared according to the present invention have excellent dielectric characteristics and electric insulation properties.
  • the copolymeric polyimide thin films which have a high dielectric strength of not less than 1 ⁇ 10 6 V/cm even if the thickness is less than 1,000 ⁇ .
  • the copolymeric polyimide thin films have a heat resistance of more than 400° C., and some films among them have a heat resistance of more than 450° C.
  • the films with a thickness of about 10,000 ⁇ having good physical properties can be realized by the LB method, but when the preparation cost is taken into consideration, the thinner, the more inexpensive, and also from the viewpoint of utilization, thin films which cannot be prepared by other methods are of interest.
  • films having a thickness of not more than 2,000 ⁇ especially films having a thickness of not more than 1,000 ⁇ or of several hundreds of angstroms or films having a thickness of 5 to 100 ⁇ , have a possibility of new interesting applications.
  • copolymeric polyimide thin films having a dielectric strength of not less than 1 ⁇ 10 6 V/cm which can be sufficiently utilized in the electronic field.
  • unique effects produced by film thickness e.g. tunnel effect, are expected, and many attractive applications utilizing them become possible.
  • Such a thin polyimide film can also be formed by spin coating or vapor deposition, but a highly skilled technique is required in achieving a dielectric strength of not less than 1 ⁇ 10 6 V/cm even with a thickness of more than 1 ⁇ m. Accordingly, it is to be understood that by the existing techniques, it is difficult to form copolymeric polyimide thin films with a thickness of not more than 1,000 ⁇ having a dielectric strength of not less than 1 ⁇ 10 6 V/cm as obtained by the present invention.
  • thin films obtained by partial conversion into polyimide under mild conditions rather than complete conversion also have a good heat resistance of more than 200° C. and excellent chemical resistance, mechanical strength and electric insulating properties.
  • the partially converted films are of course very thin films with a thickness of not more than 10,000 ⁇ , and it is possible to provide films having a thickness, e.g. 5,000 ⁇ , 2,000 ⁇ or 10 to 1,000 ⁇ .
  • the partially converted films are inferior in heat resistance to the complete polyimide films, but the electric insulation and dielectric characteristics thereof are rather superior to the complete polyimide films because the long chain alkyl groups remain.
  • the thin films of the present invention can be used in various fields of art such as electronics, energy conversion and material separation.
  • the thin films obtained according to the present invention are usable as optical recording film, resist film, insulation film, thin film for capacitors, liquid crystal orientation film, polarization film, and sensor film.
  • the thin films of the invention are useful as insulation films for IC and LSI and can be used as insulation films in electric and electronic devices having MIS or MIM structure wherein various semiconductors and metals are combined with insulation films, e.g. field effect transistor, photoelectric device, light emitting device, light receiving device, light detecting device, and therminonic transistor.
  • the thin films of the present invention are useful for use in MIS and MIM devices utilizing the tunnel effect and are usable as insulation films for JJ (Josephson junction).
  • the precursors of the invention are suitable as protective coating materials in various fields.
  • various functionalities can be revealed and the uses utilizing them are considered.
  • photoelectric devices and biosensors can be fabricated by forming films containing pigments or enzymes.
  • a flask was charged with 2.18 g (0.01 mole) of pyromellitic dianhydride (benzene-1,2,4,5-tetracarboxylic dianhydride) and 5.40 g (0.02 mole) of stearyl alcohol, and they were reacted about 100° C. for 3 hours in a dry nitrogen stream.
  • pyromellitic dianhydride benzene-1,2,4,5-tetracarboxylic dianhydride
  • IR spectrum of the product measured by KBr disk method is shown in FIG. 1. Characteristic absorptions of ester, amido I, II and III absorption bands, alkyl chain and ether are observed in the spectrum. A broad absorption (non-association) of amide group (--CONH 2 ) in 2,5-diaminobenzamide was observed at from 1670 to 1700 cm -1 in the copolymer obtained in Example 1.
  • the number average molecular weight of the product measured by using a chloroform/N,N-dimethylacetamide mixed solvent in a volume ratio of 8:2 was about 25,000 (calculated in terms of polystyrene).
  • the thermal analysis (TGA and DTA) of the amphiphilic polyimide precursor having no 2,5-diaminobenzamide was carried out in the same manner as in Example 1.
  • the results showed approximately the same behavior as those of the copolymer obtained in Example 1 by the temperature of 500° C., but the weight loss of 15% occurred by maintaining the temperature of 550° C. for 30 minutes.
  • Example 1 In a distilled chloroform/dimethylacetamide mixed solvent in a volume ratio of 8:2 was dissolved in 55.1 mg of the product obtained in Example 1 to give 25 ml of a solution of the precursor to be used for forming the LB film.
  • the obtained solution was spread onto the surface of bidistilled water, and the relationship between the surface pressure ( ⁇ ) and the area per recurring unit (unit) was measured at 20° C.
  • the surface pressure suddenly increased from about 75 ⁇ 2 /unit and a good condensed film was formed.
  • the limiting area was 60 ⁇ 2 /unit, and the collapse pressure was 55 dyne/cm which was very high for a polymer film.
  • a built-up film of 15 layers was formed on an aluminum evaporated glass substrate according to the LB method at a speed of 10 mm/minute, while maintaining the surface pressure of the monolayer on the water surface at 25 dyne/cm at 20° C. It was confirmed that the built-up film was a Y-type film from the area-time curve.
  • Precursor was prepared in the same manner as in Example 1 using 3.80 g (5 mmole) of distearyl pyromellitate, 1.19 g (10 mmole) of thionyl chloride and 0.756 g (5 mmole) of 2,5-diaminobenzamide to give about 3.6 g of light yellow powder.
  • IR spectrum of the product measured by KBr disk method is shown in FIG. 4. Characteristic absorptions of ester, amide I, II, and III absorption bands, alkyl chain and ether are observed in the spectrum. An absorption of amide group (--CONH 2 ) in 2,5-diaminobenzamide was observed at from 1670 to 1700 cm -1 in the precursor obtained in Example 2.
  • the number average molecular weight of the product measured in the same manner as in Example 1.
  • the copolymer had the number molecular weight of 20,000 (calculated in terms of polystyrene).
  • the solution of the precursor to be used for forming the LB film was prepared in the same manner as in Example 2 except that the produce obtained in Comparative Example 2 was used.
  • the obtained solution was spread onto the surface of bidistilled water, and the relationship between the surface pressure ( ⁇ ) and the area per recurring unit (unit) was measured at 20° C.
  • the surface pressure suddenly increased from about 80 ⁇ 2 /unit and a good condensed film was formed.
  • the limiting area was 65 ⁇ 2 /unit, and the collapse pressure was 45 dyne/cm which was very high for a polymer film.
  • a build-up film of 15 layers of the mixture of the product obtained in Comparative Example 2 and stearyl alcohol in a molecular ratio of 1:1 was formed on Al evaporated glass substrate according to the LB method at a speed of 10 mm/minute, while maintaining the surface pressure of the monolayer on the water surface at 25 dyne/cm at 20° C. It was confirmed that the built-up film was a Y-type film from the area-time curve.
  • the capacitance was measured at room temperature and at a frequency of 120 Hz, and the inverse capacitance values (1/C) were plotted with respect to the number of layers (M). The result is shown in FIG. 7. As shown in FIG. 7, the relationship between 1/C and M is excellent.
  • Example 2 With respect to a monomolecular film of the product obtained in Example 1 having a thickness of about 27 ⁇ , there was applied an electric field of not less than 1 ⁇ 10 6 V/cm, but no dielectric breakdown occurred.
  • IR spectrum of the product measured by KBr disk method is shown in FIG. 9. Characteristic absorptions of ester, amido I, II and III absorption bands, alkyl chain and ether are observed in the spectrum alike the polyimide precursor previously proposed by us. However, an absorptions of amido I and II (--CONH 2 ) were observed at 1680 and 1635 cm -1 according to a difference spectrum of the copolymer obtained in Example 5 and the polyimide precursor previously proposed by us.
  • TGA and DTA were conducted by the RTG-DTA(H) type analyzer with full scale 10 mg for TGA and 100 ⁇ V for DTA by elevating the temperature at a rate of 10° C./minute to 1,000° C. in a nitrogen stream (30 ml/minute). The results are shown in FIG. 10.
  • the number average molecular weight of the product measured in the same manner as in Example 1 was about 20,000 (calculated in terms of polystyrene).
  • Example 5 In a distilled chloroform/dimethylacetamide mixed solvent in a volume ratio of 8:2 was dissolved in the product obtained in Example 5 to give a solution of the precursor to be used for forming the LB film.
  • the obtained solution was spread onto the surface of bidistilled water, and the relationship between the surface pressure ( ⁇ ) and the area per recurring unit (unit) was measured at 20° C.
  • the relationship between the surface pressure ( ⁇ ) and the area per recurring unit (unit) is shown in FIG. 11.
  • the surface pressure suddenly increased from about 75 ⁇ 2 /unit and a good condensed film was formed.
  • the limiting area was 57 ⁇ 2 /unit, and the collapse pressure was 47 dyne/cm which was very high for a polymer film.
  • a built-up film could be formed on an aluminum evaporated glass substrate by using a mixture of the precursor and stearyl alcohol according to the LB method at a speed of 10 mm/minute, while maintaining the surface pressure of 25 dyne/cm at 20° C., and it was confirmed that the obtained built-up film was a Y-type film.
  • Example 5 With respect to a monomolecular film of the product obtained in Example 5 having a thickness of about 27 ⁇ , there was applied an electric field of not less than 1 ⁇ 10 6 V/cm, but no dielectric breakdown occurred.
  • the copolymeric and amphiphilic polyimide precursor of the present invention can provide thin films by the LB technique, and by ring closure such as imidizing of the obtained LB films, there can be obtained ultrathin films having excellent heat resistance, electric properties, chemical resistance and mechanical properties, and having a thickness of not more than 10,000 ⁇ , and if desired, a thickness of 10 to 1,000 ⁇ . Further, the process of the present invention has such an advantage that polyimide thin films having a wide range of properties can be easily prepared. When a part of the group R 2 in the precursor of the present invention are substituted with a trivalent or tetravalent group, the heat resistance of the precursor can be improved since a ring having better heat resistance than an imide ring is formed.

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US5246784A (en) * 1990-10-09 1993-09-21 Basf Aktiengesellschaft Ultrathin thermostable bismaleimide films and production thereof
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EP0452986A3 (en) * 1986-09-04 1991-12-18 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Photosensitive amphiphilic high molecular weight polymers and process for their production
JPS6372375A (ja) * 1986-09-12 1988-04-02 Kanegafuchi Chem Ind Co Ltd 両性高分子化合物およびその製造法
EP0355927B1 (fr) * 1988-08-24 1994-11-23 Asahi Kasei Kogyo Kabushiki Kaisha Précurseur d'un polyimide à contraintes thèrmiques faibles et composition photopolymèisable contenant un précurseur de polyimide
US5120573A (en) * 1988-09-28 1992-06-09 Hitachi, Ltd. Process for producing metal/polyimide composite article
JPH07102646B2 (ja) * 1988-09-30 1995-11-08 株式会社日立製作所 金属とポリイミドの複合成形体
DE4115872A1 (de) * 1991-05-15 1992-11-19 Basf Ag Verfahren zur herstellung duenner polyimidschutzschichten auf keramischen supraleitern oder hochtemperatursupraleitern
US9492841B2 (en) * 2012-03-20 2016-11-15 Imec Method for pore sealing of porous materials using polyimide langmuir-blodgett film
JP6038058B2 (ja) * 2014-02-26 2016-12-07 富士フイルム株式会社 ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5135678A (en) * 1988-10-05 1992-08-04 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Liquid crystal device
US5246784A (en) * 1990-10-09 1993-09-21 Basf Aktiengesellschaft Ultrathin thermostable bismaleimide films and production thereof
US5260004A (en) * 1991-12-02 1993-11-09 The United States Of America As Represented By The Secretary Of The Army Process of making Langmuir-Blodgett films having photo-electronic properties

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EP0247358A3 (fr) 1990-09-12
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JPS6346227A (ja) 1988-02-27
EP0247358A2 (fr) 1987-12-02

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